Nylon polymers blended with cyclic ester polymers

ABSTRACT

UNIFORM, THERMOPLASTIC, NORMALLY SOLID BLENDS CONTAINING CYCLIC ESTER POLYMERS CONTAINING RECURRING UNITS OF THE FORMULA   -(O-(C(-R)2)X-(A)Z-(C(-R)2)Y-CO)-   WHEREIN EACH R, INDIVIDUALLY, IS SELECTED FROM THE CLASS CONSISTING OF HYDROGEN, ALKYL, HALO, AND ALKOXY; A IS THE OXY GROUP; X IS AN INTEGER OF ZERO OR ONE; WITH THE PROVISOS THAT (A) THE SUM OF X+Y+Z IS AT LEAST 4 AND NOT GREATER THAN 7, AND (B) THE TOTAL NUMBER OF R VARIABLES WHICH ARE SUBSTITUENTS OTHER THAN HYDROGEN DOES NOT EXCEED 3, WITH OR WITHOUT RECURRING UNITS OF THE FORMULA   -O-CH(-R&#39;&#39;)-CH(-R&#39;&#39;)-   WHEREIN EACH R&#39;&#39; IS SELECTED FROM THE CLASS CONSISTING OF, INDIVIDUALLY, HYDROGEN, ALKYL, CYCLOALKYL, ARYL, AND CHLOROALKYL, AND TOGETHER WITH THE ETHYLENE MOIETY OF THE OXYETHYLENE CHAIN OF UNIT II, A SATURATED CYCLOALIPHATIC HYDROCARBON RING HAVING FROM 4 TO 8 CARBON ATOMS, AND THERMOPLASTIC, NORMALLY SOLID POLYMER WHICH CAN BE A CONDENSATION POLYMER, AND/OR AN ADDITION POLYMER OF OLEFINICALLY UNSATURATED MONOMERS HAVING NO MORE THAN ONE HYDROGEN BONDED TO EACH CARBON OF EACH OLEFINICALLY UNSATURATED GROUP THEREOF, INCLUDING SUCH POLYMERS AS CELLULOSE DERIVATIVES, NYLONS, POLYESTER POLYMERS, POLYOXYALKYLENES, POLYCARBONATES. POLY(FLUOROCARBONS), COUMARONE-INDENE RESINS, MALEIC ACID OR ANHYDRIDE ADDITION POLYMERS AND COPOLYMERS, STILBENE ADDITION POLYMERS AND COPOLYMERS, CHLORINATED POLYETHERS, AROMATIC POLY(HYDROXY ETHER) POLYMERS, POLYSULFONES, POLYPEPTIDES, ETC. THESE NOVEL BLENDS ARE USEFUL IN THE PRODUCTION OF FIBERS, FILMS, COATINGS, ADHESIVES, WIRE AND CABLE COATINGS, MOLDING MATERIALS, EXTRUSION MATERIALS, OR SHAPED ARTICLES, HAVING ONE OR MORE UNIQUE PROPERTIES, SUCH AS, DYEABILITY, IMPROVED STRESS CRACK RESISTANCE, IMPROVED OPTICAL PROPERTIES, E.G., IMPROVED HIDING POWER, LOW HAZE, HIGH GLOSS AND/OR HIGH LIGHT TRANSMISSION, IMPROVED PLASTICIZATION, IMPROVED TOUGHNESS, IMPROVED MELT PROCESSABILITY, IMPROVED IMPACT RESISTANCE, AND/OR IMPROVED ABILITY TO DISPERSE ADDITIVES, SUCH AS, FILLERS, COLORING AGENTS, ANTIOXIDANTS, EXTENDERS, ETC.

United States Patent US. Cl. 260-857 PE 12 Claims ABSTRACT OF THEDISCLOSURE Uniform, thermoplastic, normally solid blends containingcyclic ester polymers containing recurring units of the formula l /t l L\R/. W. .I

wherein each LR, individually, is selected from the class consisting ofhydrogen, alkyl, halo, and alkoxy; A is the oxy group; x is an integerfrom 1 to 4; y is an integer from 1 to 4; z is an integer of zero orone; with the provisos that (a) the sum of X+y+z is at least 4 and notgreater than 7, and (b) the total number of R variables which aresubstituents other than hydrogen does not exceed 3, with or withoutrecurring units of the formula (II) R R wherein each R is selected fromthe class consisting of, individually, hydrogen, alkyl, cycloalkyl,aryl, and chloroalkyl, and together with the ethylene moiety of theoxyethylene chain of Unit II, a saturated cycloaliphatic hydrocarbonring having from 4 to 8 carbon atoms, and thermoplastic, normally solidpolymer which can be a condensation polymer, and/or an addition' polymerof olefinically unsaturated monomers having no more than one hydrogenbonded to each carbon of each olefinically unsaturated group thereof,including such polymers as cellulose derivatives, nylons, polyesterpolymers, polyoxyalkylenes, polycarbonates, poly(fluorocarbons),coumarone-indene resins, maleic acid or anhydride addition polymers andcopolymers, stilbene addition polymers and copolymers, chlorinatedpolyethers, aromatic poly(hydroxy ether) polymers, polysulfones,polypeptides, etc.

These novel blends are useful in the production of fibers, films,coatings, adhesives, Wire and cable coatings, molding materials,extrusion materials, or shaped articles, having one or more uniqueproperties, such as, dyeability, improved stress crack resistance,improved optical properties, e.g., improved hiding power, low haze, highgloss and/or high light transmission, improved plasticization, improvedtoughness, improved melt processability, improved impact resistance,and/or improved ability to disperse additives, such as, fillers,coloring agents, antioxidants, extenders, etc.

This application is a continuation-in-part of application Ser. No.812,314, now abandoned, entitled, Uniform, Thermoplastic, Normally SolidCompositions Containing Diverse Components, by J. V. Koleske, C. I.Whitworth, Jr., and R. D. Lundberg, filed Apr. 1, 1969; both of theaforesaid applications being assigned to a common assignee.

'7 r 3,781,381 Patented Dec. 25, 1973 F is.

BACKGROUND OF THE INVENTION (a) Field of the invention The presentinvention relates to novel uniform, thermoplastic, normally solidpolymer blends containing normally solid, thermoplastic polymers, suchas, condensation polymers and addition polymers of olefiniciallyunsaturated monomers having no more than one hydrogen bonded to eachcarbon of each olefinically unsaturated group thereof, in intimateassociation with cyclic ester polymers, such as polymer ofepsilon-caprolactone, and having a Wide range of application in theproduction of fibers, films, and other shaped articles. As used herein,the term polymer includes homopolymers, copolymers, terpolymers, etc.,and, in general, a polymer made by polymerizing any number of monomers.

(b) Description of the prior art Thermoplastic polymers in the nature ofnormally solid condensation polymers and addition polymers of the typedescribed herein including cellulose derivatives, nylons or polyamides,polypeptides, polyoxyalkylenes, polycarbonates, polyurethanes,polysulfones, poly(hydroxy ether) polymers, polyimides, polyureas,polyester polymers, maleic anhydride copolymers, stilbene homopolymersand copolymers, and the like have been long known and extensively usedin the manufacture of household articles, industrial and commercialarticles, wearing apparel, adhesives, molding compositions, extrusioncompositions, protective coatings, wire and cable coatings, conduits,hoses and a wide variety of other articles. While such heretofore knownthermoplastic, normally solid polymers possess important and uniqueproperties which enhance their widespread use for a great manyapplications, there has been a need to modify or correct certainundesirable properties in order to widen the field of use of suchmaterials or to improve their current field of application.

For example, many of these thermoplastic polymers would be chosen for aparticular use on the basis of their peculiar properties, except thatthey may be too stifi and difiicult to shape and form or they may needimprovement in other areas such as stress crack resistance, impactresistance, or optical properties. Another area of potentialimprovements by modification is in the melt processibility of thethermoplastic polymers, especially when using additives, such as,fillers, pigments, dye stuffs, anti-oxidants, stabilizers and others tobe blended into the polymers. Due to the high viscous and sticky natureof the thermoplastic polymers during processing, it is sometimesextremely difficult to disperse the additives uniformly throughout thepolymer.

Attempts to prepare useful polymeric blends of two or more polymers havegenerally been unsuccessful. Blends of diiferent types of polymers areoften incompatible, and this incompatibility usually results in a markeddeterioration or loss of the physical properties characteristic of eachof the unblended polymers. Even where the two polymers are compatible inthe melt, they often tend to separate into segregated domains of eachindividual polymer species. This segregation into separate domainsresults in a non-uniform mass and usually results in a markeddeterioration of the physical properties which would be characteristicof either of the unblended polymers or copolymers.

Because of these factors, a large technology of copolymers has developedemploying comonomers with varying degrees of success. By proper choiceof such comonomers, copolymerization of different chemical units withinthe same polymer chain can be achieved to give some desirable propertiesin certain specific instances. Physical mixing or blending of themodifier, because of its simplicity and ease of performance, ispreferred over the chemical or copolymerizing technique but has not beenheretofore achievable over a wide range of the diverse thermoplasticpolymers known and described herein. This invention now permits theblending of a wide range of diverse thermoplastic normally solidpolymers with cyclic ester polymers to form uniform polymer blendshaving useful and desirable properties over a broad composition range.It is believed that the presence of the cyclic ester polymer lessenssegregation of the two polymers into separate domains and prevents thesignificant loss of physical properties which would be associated withsuch segregation.

Usually when one mixes or blends polymers, incompatibility is theexpected result and compatibility of the polymers is not expected unlessvery small amounts of one of the components are added or if the polymersare very similar in nature as, for example, high and low densitypolyethylene. However, in certain instances blends of polymers can havecommercial utility but in most cases the blended polymers had to besimilar in nature or present in very small amounts to be compatible andno one polymer was blended with a wide range of diverse polymers withthe possible exception of nitrocellulose. As summarized in Principles ofPolymer Chemistry, Paul I. Flory, Cornell University Press, Ithaca,N.Y., 1953, at page 555, incompatibility of chemically dissimilarpolymers is observed to be the rule and compatibility is the exception.

SUMMARY OF THE INVENTION The present invention provides novel uniform,thermoplastic polymeric blends and provides a means for readily alteringthe properties of such important plastics as thermoplastic, normallysolid condensation polymers including polyoxyalkylenes, polycarbonates,cellulose esters, cellulose ethers, polyurethanes, polysulfones,polyamides, e.g., nylons, poly(hydroxy ethers), polyimides, polyureas,polyester polymers, and addition polymers of olefinically unsaturatedmonomers having no more than one hydrogen on each carbon of eacholefinically unsaturated group thereof, to impart highly desirableproperties not easily obtained in such plastics prior to this invention.

Heretofore, it was the case that, in many instances, when a polymericmodifier was attempted to be added to thermoplastic polymers of thesetypes, the polymers would not accept the polymeric modifier and thereresulted nonuniform masses and non-uniform, deteriorated properties.

This is not the case with the novel thermoplastic, normally solidcompositions of this invention which contain cyclic ester polymersuniformly blended throughout with a thermoplastic, normally solidpolymer. Unlike the previous attempts to form uniform blends of suchthermoplastics with substantial amounts of polymeric modifiers, thethermoplastic polymers readily accept the cyclic ester polymer blendedtherein through the present invention. This ease of acceptance of cyclicester polymers is surprising in that it applies throughout a. diverserange of thermoplastic polymers to provide diverse improvements in theproperties of the thermoplastic polymer. Despite the presence of cyclicester polymer uniformly blended in the thermoplastic polymer, itsbeneficial properties are not greatly affected.

When the cyclic ester polymer is added and blended with thethermoplastic polymer, the processability of the thermoplastic polymeris considerably improved. Not only are the milling characteristics ofthe thermoplastic enhanced, but also additives, such as fillers,accelerators, coloring agents, and other common plastic additives aremore readily dispersed throughout the mass of the thermoplastic.

The handling and shaping of the novel thermoplastic, normally solidcompositions to fabricate shaped articles are also facilitated. Thenovel compositions are more readily spread to conform to theconfiguration of molds and can be formed into sheets or other shapeswhich are easier to handle and fabricate in the desired manner in thesoft or molten stage. The novel compositions possess other advantageswhich will appear hereinafter on a case by case basis.

The cyclic ester polymers which are contemplated in the practice of theinvention are those which possess a reduced viscosity value of at leastabout 0.1, and desirably from about 0.2 to about 15, and higher. Thepreferred polymers of cyclic esters for many applications have a reducedviscosity value of from about 0.3 to about 5. These polymers are furthercharacterized by the following recurring structural linear Unit I:

can. at

wherein each R, individually, is selected from the class consisting ofhydrogen, alkyl, halo and alkoxy; A is the oxy group; x is an integerfrom 1 to 4; y is an integer from 1 to 4; z is an integer of zero orone; with the provisos that (a) the sum of x+y+z is at least 4 and notgreater than 7, and (b) the total number of R variables which aresubstituents other than hydrogen does not exceed 3, preferably does notexceed 2, per unit. Illustrative R variables include methyl, ethylisopropyl, n-butyl, secbutyl, t-butyl, hexyl, chloro, bromo, iodomethoxy, ethoxy, n-butoxy, n-hexoxy, 2-ethylhexoxy, dodecoxy, and thelike. It is preferred that each R, individually, be hydrogen, loweralkyl, e.g., methyl, ethyl, n-propyl, isobutyl, and/or lower alkoxy,e.g. methoxy, ethoxy, propoxy, nbutoxy, and the like. It is furtherpreferred that the total number of carbon atoms in the R substituentsdoes not exceed twenty.

In one embodiment, highly desirable cyclic ester polymers which arecontemplated are characterized by both recurring structural Unit I supraand recurring structural Unit II:

Tonal L E f it .I

wherein each R is selected from the class consisting of, individually,hydrogen, alkyl, cycloalkyl, aryl, and chloroalkyl, and, together withthe ethylene moiety of the 0x0- ethylene chain of Unit II, a saturatedcycloaliphatic hydrocarbon ring having from 4 to 8 carbon atoms,desirably from 5 to 6 carbon atoms. It is preferred that recurring UnitII contains from 2 to 12 carbon atoms. Illustrative R variables includemethyl, ethyl, n-propyl, isoproyl, t-butyl, the hexyls, the dodecyls,2-chloroethyl phenyl, phenethyl, ethylphenyl, cyclopentyl, cyclohexyl,cycloheptyl, and the like. It is preferred that R be hydrogen; loweralkyl, e.g., methyl, ethyl, n-propyl, isopropyl; chloroalkyl, e.g.,2-chloroethyl; and the like.

The aforedescribed recurring linear unit (I) is interconnected throughthe oxy group (-O) of one unit with the carbonyl group of a second unit.In different language, the interconnection of these units does notinvolve the direct bonding of two carbonyl groups, i.e.,

O 0 & .l

With relation to the relatively high molecular weight cyclic esterpolymers, the terminal moieties thereof are not determinable by infraredanalysis which factor is readily understandable since macromolecules areinvolved. On the other hand, the relatively lower molecular weightcyclic ester polymers, e.g., those having reduced viscosity values belowabout 0.25 are characterized by end groups which can be hydroxyl;arboxyl, hydrocarbyl, such as, alkyl, cycloalkyl, aryl, aralkyl, andalkaryl; hydrocarbyloxy, such as, alkoxy, cycloalkoxy; aryloxy,aralkoxy, and alkaryloxy; and possibly other moieties such as catalystresidue; and mixtures of the foregoing. It may be desirable in certaininstances that the hydroxyl and carboxyl end groups, if present, beesterified or acylated to render them inert such as by reacting thehydroxyl moiety with a monocarboxyl compound or its correspondinganhydride, e.g., acetic acid, acetic amhydried, butyric acid,Z-ethylhexanoic acid, benzoic acid, etc., or by reacting the carboxylmoiety with a monohydroxyl compound such as a monohydric alcohol ormonohydric phenol, e.g., methanol, 2-ethylhexanol, isobutanol, phenol,and the like.

When the cyclic ester polymers are prepared from a mixture containingthe cyclic ester monomer and a cyclic ether which is copolymerizabletherewith, e.g., alkylene oxide, oxetane, tetrahydrofuran, etc., thepolymeric chain of the resulting copolymeric product will becharacterized by both recurring linear Unit I supra as well as therecurring linear Unit II which would represent the alkylene oxidecomonomer polymerized therewith. When the comonomer is an alkyleneoxide, then the resulting copolymeric product will contain bothrecurring linear Unit I and recurring linear Unit II in the copolymericchain thereof. The interconnection of linear Unit I and linear Unit 11supra does not involve or result in the direct bonding of two oxygroups, i.e., OO. In other words, the oxy group (-O-) of recurringlinear Unit II is interconnected with the carbonyl group of recurringlinear Unit I supra or with the alkylene moiety of a second oxyalkyleneUnit (II).

Particularly preferred polymers of cyclic esters are those which arecharacterized by the oxypentamethylenecarbonyl chain as seen inrecurring structural Unit III:

Lilith wherein each R is hydrogen or lower alkyl, preferably hydrogenor. methyl, with the proviso that no more than three R variables aresubstituents other than hydrogen.

The preparation of the cyclic ester polymers is well documented in thepatent literature as exemplified by U.S. Pats. Nos. 3,021,309 through3,021,317; 3,169,945; and 2,962,524, and Canadian Pat. No. 742,294.Briefly, the process involves the polymerization of an admixturecontaining at least one cyclic ester monomer with or without afunctional (e.g., active hydrogen-containing) initiator therefor, and asuitable catalyst, the choice of which will depend on the presence orabsence of added initiator.

Suitable monomeric cyclic esters which can be employed in themanufacture of the cyclic ester polymers are best illustrated by thefollowing formula:

wherein the R, A, x, y, and z variables have the significance noted inUnit I supra.

Representative monomeric cyclic esters which are contemplated include,for example, delta-valerolactone; epsilon-caprolactone;zeta-enantholactone; eta-caprylolactone; themonoalkyl-delta-valerolactones, e.g., the monomethyl, monoethyl-,monohexyl-, deltavalerolactones, and the like; thedialkyl-delta-valerolactones, e.g., the dimethyl-, diethyl-, anddi-n-octyl-delta-valerolactones, and the like; the monoalkyl-, dialkyl-,and trialkyl-epsilon-caprolactones, e.g., the monomethyl-, monoethyl-,monohexyl-, dimethyl-, diethy1-, di-n-propyl-, di-n-hexyl-, trimethy1-,

triethyl-, and tri-n-propyl-epsilon-caprolactones, and the like; themonoalkoxyand dialkoxy-delta-valerolactones and epsilon-caprolactones,e.g., the monomethoxy-, monoisopropoxy-, dimethoxy-, anddiethoxy-delta-valerolactones and epsilon-caprolactones, and the like;1,4-dioxane- 2-one; dimethyl-1,4-dioxane-2-one, and the like. A singlecyclic ester monomer or mixtures of such monomers may be employed.

In the absence of added functional initiator, the polymerization processis desirably effected under the operative conditions and in the presenceof anionic catalysts as noted in U.S. Pats. Nos. 3,021,309 to 3,021,317,such as, dialkylzinc, dialkylmagnesium, dialkylcadmium,trialkylaluminum, dialkylaluminum alkoxide, alkylaluminum dialkoxide,dialkylaluminum halide, aluminum trialkoxide, alkyllithium, andaryllithium. Specific anionic catalysts would includue di-n-butylzinc,diethylmagnesium, di-nbutylrnagnesium, dimethylcadmium, diethylcadmium,dit-butylcadmium, triethylaluminum, triisobutylaluminum,tri-2-ethylhexylaluminum, aluminum triisopropoxide, aluminumtriethoxide, ethyllithium, n-butyllithium, phenyllithium, and the like.

When employing an admixture containing cyclic ester monomer andfunctional initiator which possesses at least one active hydrogensubstituent, e.g., amino, carboxyl, and hydroxyl, it is desirable to usethe catalysts noted in U.S. Pats. Nos. 2,878,236, 2,890,208, 3,169,945,and 3,284,417 under the operative conditions discussed therein. In theseprocesses the active hydrogen substituent on the initiator is capable ofopening the monomer cyclic ester ring whereby said cyclic ester is addedto said initiator as a substantially linear group thereto. The molecularWeight of the resulting polymers of cyclic ester can be predetermined bycontrolling the molar ratios of cyclic ester monomer to be added to thefunctional initiator. Amino and hydroxyl substituents on the initiatorwill result in polymeric products having hydroxyl end group. Carboxylsubstituents on the initiator will result in polymeric products havingcarboxyl end-group. The initiator with the active hydrogen atom Willthus be contained in the final polymeric molecule. The esterification oracylation of the afore-mentioned end-groups has been describedpreviously and is voluminously documented in the art.

Polymers of cyclic esters can also be manufactured via the processdescribed in U.S. Pat. No. 2,962,524. In this process, a monomericadmixture comprising cyclic ester and alkylene oxide which desirably hasthe formula:

wherein each R, individually, has the meanings noted in Unit II supra,can be reacted with a monofunctional and/or polyfunctional (e.g., activehydrogen-containing) initiator possessing amino, hydroxyl, and/orcarboxyl groups, preferably in the presence of a Lewis acid catalystsuch as boron trifluoride. Illustrative alkylene oxides would includeethylene oxide, propylene oxide, the butylene oxides, styrene oxide,epichlorohydrin, cyclohexene oxide and the like.

Cyclic ester/alkylene oxide copolymers can also be prepared by reactingin the absence of an active hydrogen-containing initiator an admixturecomprising cyclic ester and alkylene oxide monomers, an interfacialagent such as a solid, relatively high molecular weight poly (vinylstearate) or lauryl methacrylate/vinyl chloride copolymer (reducedviscosity in cyclohexanone at 30 C. of from about 0.3 to about 1.0), inthe presence of an inert normally-liquid saturated aliphatic hydrocarbonvehicle such as heptane, phosphorus pentafluoride as the catalysttherefor, at an elevated temperature, e.g., about C. and for a period oftime suflicient to produce such cyclic ester/alkylene oxide copolymers.

The cyclic ester polymers employed herein contain in the polymeric chainat least a major molar amount, i.e., greater than about 50, preferablyabout 80, to about mol percent of Units I and up to a minor molaramount, i.e., about to less than about 50, preferably up to about 20,mol percent of other units such as alkylene oxide Units II, initiatorresidues or moieties, catalyst residues, and other difunctional and/ormonofunctional units. The cyclic ester polymers containing about 100 molpercent of Unit I are preferred and those in which Unit I represents theoxypentamethylene carbonyl moiety are most preferred. In variousdesirable embodiments there can be employed cyclic ester polymers whichcontain from 100 to about mol percent of Units I supra and from 0 toabout 90 mol percent of Units II supra in the polymeric chains thereof.

As mentioned previously, the polymers of cyclic esters which arecontemplated are expressed in terms of their reduced viscosity values.As is well known in the art, reduced viscosity value is a measure orindication of the molecular weight of polymers. The expression reducedviscosity is a value obtained by dividing the specific viscosity by theconcentration of polymer in the solution, the concentration beingmeasured in grams of polymer per 100 milliliters of solvent. Thespecific viscosity is obtained by dividing the difference between theviscosity of the solution and the viscosity of the solvent by theviscosity of the solvent. Unless otherwise noted, the reduced viscosityvalues herein referred to are measured at a concentration of 0.2 gram ofpolymer in 100 milliliters of benzene (benzene is preferred althoughcyclohexanone, chloroform, toluene or other organic solvent for thepolymer may be used) at 30 C.

Mixtures of homopolymers and/or copolymers, terpolymers etc., made fromdifferent cyclic esters can be employed in this invention.

The cyclic ester polymer can be fluxed on a mill and sheeted olf to formsheets or films. It can be extruded as a tape, rope, or other shape orcan be extruded and pelletized. When formed by the dispersionpolymerization technique, the cyclic ester polymer is obtained in powderor granular form. It can also be dissolved in a suitable solvent, suchas, benzene, toluene, 2-nitropropane, methylene chloride and othersolvents. Methylene chloride and other fast drying solvents may bepreferred when the cyclic ester is used as a solution. Although thecyclic ester polymer can be used in this invention in any of theabove-mentioned forms, it is usually preferred to use it in the form ofpowders, granules or pellets.

The thermoplastic organic polymer component of the novel blendsdisclosed and claimed herein are well known to those skilled in theplastics art. For the purposes of this invention the thermoplasticpolymers are classified into two categories; namely, thermoplasticcondensation polymers other than the cyclic ester polymers disclosedherein, and thermoplastic addition polymers, including copolymers,terpolymers, etc., of polymerizable olefinically unsaturated monomershaving not more than one hydrogen bonded to each carbon of eacholefinically unsaturated group thereof.

The term condensation polymers as used herein is consistent with thepolymer classification set forth in Principles of Polymer Chemistry, byPaul J. Flory, Cornell University Press, Ithaca, N.Y., 1953, at pages37-50 and 57-61, and particularly in the paragraph bridging pages 39 and40 and the one bridging pages 57 and 59. Thus, the term is not limitedto those polymers which are produced with concurrent evolution of lowmolecular weight substances, such as, water, HCl, NaCl and the like, butalso include polymers produced by polymerization with no evolution oflow molecular weight by-prodnets and which contain interunit linkagesnot found in the monomers, e.g., the polyurethanes, polyureas, and thelike, and to polymers produced by the addition polymerization of cyclicmonomers, e.g., polyoxyalkylenes, chlorinated polyoxyalkylenes,polyimides, polylactams and the like. Suitable condensation polymersalso include derivatives, i.e., the ethers and esters, of cellulosewhich L CH: Another class of thermoplastic condensation polymerssuitable for use herein is the polycarbonate class, prefer: ablyaromatic polycarbonates derived from aromatic dihydroxy compounds orphenols having 6 to 24 carbon atoms and phosgene. An illustration is thepolycarbonate made by reacting phosgene with bisphenol A and having therecurring unit CH L (7H3 y) Another class of thermoplastic condensationpolymers is the polysulfones, preferably the aromatic polysulfonesderived from aromatic dihydroxy compounds having 6 to 24 carbon atomsand di(chloroaryl) sulfones. An illustration is the polysulfone made byreacting bisphenol A and di(parachlorophenyl) sulfone and having therecurring unit of the formula:

The thermoplastic cellulosic esters and ethers are widely used asmolding, coating and film-forming materials and are well known. Thesethermoplastic condensation polymers can also be used as thethermoplastic component in the practice of this invention. Thesematerials include the solid thermoplastic forms of cellulose nitrate,cellulose acetate (e.g., cellulose diacetate, cellulose triacetate),cellulose butyrate, cellulose acetate butyrate, cellulose propionate,cellulose tridecanoate, carboxymethyl cellulose, ethyl cellulose,hydroxyethyl cellulose and acetylated hydroxyethyl cellulose asdescribed on pages of Modern Plastics Encyclopedia, 1962, and referenceslisted therein.

Another class of thermoplastic condensation polymers is the polyamides,such as, nylon 6 (e.g., polycaprolactam), nylon 6/6, e.g.,hexamethylenediamine-adipic acid or anhydride polycondensate), nylon6/10 (e.g., hexamethylenediamine-sebacic or anhydride polycondensate),nylon 8 (e.g., N-alkoxymethylhexamethylenediamineadipic acid oranhydride polycondensate), nylon 11 (e.g., ll-aminoundecanoic acidpolycondensate) and the like as described on pages 219-227 of ModernPlastics Encyclopedia, 1962, and references listed therein. Suitable foruse herein are polyamides of hydrocarbon dicarboxylic acids having 2 to18 carbon atoms and hydrocarbon diamines having 2 to 18 carbon atoms andhomopolymers of such diamines.

Another class of thermoplastic condensation polymers is the normallysolid thermoplastic polyoxyalkylene polymers, both unsubstituted andhalogenated. The lowest homologous type of this class is thepolyoxymethylene polymers, otherwise called acetal resins, and aredescribed on pages 140-142 of Modern Plastics Encyclopedia, 1962. Inaddition, the normally solid polyoxyethylene, polyoxypropylene, andpolyoxybutylene polymers and copolymeric forms, e.g.,poly(oxyethyleneoxypropylene) copolymers wherein the oxyethylene unitsare randomly distributed or present in blocks,poly(oxymethyleneoxyethylene) copolymers andpoly(oxymethyleneoxypropylene) copolymers having a block or randomdistribution are all well known and can be employed as the thermoplasticcomponent. The halogenated polyoxyalkylene normally solid polymers arealso well known and are suitable for use in the novel blends of thisinvention. For example, the chlorinated polyethers made and sold underthe name of Penton by Hercules Powder Company (pages 171-172 ModernPlastics Encyclopedia, 1962) and having the recurring unit of theformula:

ictiillll L dmcl I as well as copolymers containing such units andoxyethylene units, CH CH O, in random or block distribution, also aresuitable as the thermoplastic component. These are made by additionpolymerization of epichlorhydrin which can be conducted with ethyleneoxide if the copolymer is desired. Other oxyalkylene units can beprovided in place of or in addition to oxyethylene by the additionpolymerization of other alkylene oxides with chlorinated oxetane (usedto produce Penton) or epichlorhydrin.

Another class of thermoplastic condensation polymers is the normallysolid polyester polymers of polyhydric, preferably dihydric, alcoholshaving 2 to 18 carbon atoms and polycarboxylic, preferably dicarboxylic,acids or acid anhydrides having 2 to 18 carbon atoms, for example, thosedescribed in pages 244-250, Modern Plastics Encyclopedia, 1962, andreferences cited therein. Examples of suitable polyester polymers arepoly(ethylene terephthalate), poly(1,3-propylene maleate), poly(ethylenefumarate), poly(diethylene phthalate), poly(2,3-butylene adipate), andthe like.

Polyurethanes, otherwise known as isocyanate resins, also can bemodified in accordance with this invention. Some of these thermoplasticcondensation polymers are described on pages 216-218 of Modern PlasticsEncyclopedia, 1962, and references cited therein. For example,polyurethanes formed from toluene diisocyanate (TD'I) or diphenylmethane 4,4-diisocyanate (MDI) and a wide range of polyols, such as,polyoxyethylene glycol, polyoxypropylene glycol, hydroxy-terminatedpolyesters, polyoxyethylene-oxypropylene glycols are suitable. The thermoplastic, normally solid polyurethanes described in Saunders & Frlsch,Polyurethanes: Chemistry And T echnology, Interscience Publishers, NewYork, Part I, Chemistry, published in 1963 and Part II, Technology,published in 1964 can be used.

The polyureas can also be advantageously modified by cyclic esterpolymers according to this invention. Suitable polyureas arethermoplastic solids having recurring units of the formula{-NHRNHCONHR"NHCO-} wherein R" is arylene having 6 to 12 carbon atoms,alkylene having 2 to 12 carbon atoms or cycloalkylene having 3 to 12carbon atoms, e.g., -ENH(CH NHCONH(CH NHCOfl-.

In the second category of thermoplastic organic polymers are theaddition polymers of olefinically unsaturated monomers having no morethan one hydrogen on each carbon atom of each olefinically unsaturatedgroup thereof, i.e., monomers having the group, C= each carbon of whichis bonded to 0 or 1 hydrogen atom but not 2. Monomers of this typeinclude maleic acid or acid anhydride, fumaric acid, stilbene,cyclohexane, cyclobutene, tetrafluoroethylene, hexafiuoropropylene,trifluoroethylene, chlorotrifluoroethylene, tetrahydrophthalic acid oracid anhydride, 3,4-dimethyl-2-pentene, terpene, 2- hexane, 3-heptene,cournarone, indene and the like. Thermoplastic, normally solidhomopolymers or copolymers of one or more monomers of the type listedabove are suitable, e.g., the fluorocarbon polymers, namely, poly-(tetrafiuoroethylene) poly (trifluoroethylene),poly(chlorotrifluoroethylene), and poly(hexafluoropropylene) describedin pages 198-202, Modern Plastics Encyclopedia, 1962, and referencescited; the cournarone-indene resins, petroleum resins and polyterpeneresins described in pages 174-175 and cited references of ModernPlastics Encyclopedia, 1962; maleic acid ar acid anhydride additionpolymers and copolymers, e.g., maleic anhydride-methyl vinyl ether,maleic anhydride-ethyl vinyl ether and maleic anhydride-isobutyl vinylether addition copolymers; stilbene addition polymers and copolymers,e.g., stilbene-acrylonitrile copolymers, and the like.

The relative proportions of cyclic ester polymer and thermoplastic,normally solid polymer employed in the novel compositions of thisinvention can be varied over very wide percentage ranges depending uponthe particular characteristic desired in the particular compositionbeing prepared and its intended use. For example, the cyclic esterpolymer can be present in amounts ranging from about 1 to about and thethermoplastic polymer component can be present in amounts ranging fromabout 5 to about 99%, based on the total weight of cyclic ester polymerand thermoplastic polymer component. It is preferred in most cases toutilize a minor amount of the cyclic ester polymer and a major amount ofthe thermoplastic polymer component. More preferably, about 2 to about40% of the cyclic ester polymer and about 60 to about 98% of thethermosplastic polymer component are employed and most preferably about5 to about 30% of the cyclic ester polymer and about 70 to about 95 ofthe thermoplastic polymer component are employed.

A surprising aspect of the present invention is the discovery thatimproved properties are obtained when even very small amounts of thecyclic ester polymer are used. It i equally, if not more, surprising tohave found that even major amounts of cyclic ester polymer, i.e., up toabout 95 weight percent, do not completely obliterate the characteristicproperties of the thermoplastic component. It is an extremely importantdiscovery of this invention that, when up to about 40% on a weight basisof cyclic ester polymer is used in the novel compositions, thereresults, in many systems, an easily processable thermoplasticcomposition which can be molded at elevated temperatures and underpressures, if desired, to form thermoplastic articles having physicalproperties very close to the physical properties of articles made fromthe thermoplastic component alone. The novel compositions containingminor amounts of cyclic ester polymer can be molded or extruded to formsheets, plaques, pellets, tapes or other articles which are non-blockingand can be stacked one upon the other without sticking together.Subsequently, they can be shaped by molding at elevated temperatures andpressures or by other means. Even relatively minor amounts such as 30%or less decrease the stiffness of most thermosplastic components andrender them less sticky and more easily worked.

The thermoplastic polymer component and cyclic ester polymer can bemixed or blended by any desired technique. For example, they can beblended on a two-roll mill, Brabender mixer, or other equipment at lowto moderate temperatures, for example, in the range of 60 C. or higher,for example, up to as high as to 250 C. However, the lower temperaturesare usually suitable and are economically preferred.

Suitable equipment for fluxing the thermosplastic component and cyclicester polymer together include Banbury mixers, Brabender mixers, screwextruders, two-roll mills, or any other mixing devices adapted to mixhighly viscous or semi-solid materials at low to moderate or hightemperatures. The time of blending or fluxing is not narrowly criticaland a suflicient blending time to obtain a substantially uniform blendis usually satisfactory. Mixing of the cyclic ester polymer and thethermoplastic component in the heated or molten state is believed to befacilitated by the partial hydrocarbon nature of the cyclic esterpolymer. Either there can be no phase separation, or the phaseseparation is such that there is no deleterious change of physicalproperties in blending the two different polymeric materials together inaccordance with this invention.

Illustrative times of blending are in the range of 1 and 2 minutes to 30minutes or an hour. In the usual case, about 5 to 15 minutes isadequate. After adequate blending, the novel thermosplastic compositionis cooled to ambient temperature and thereafter can be shaped and/orformed in any desired manner. If desired, other materials can be addedduring blending, for example, the usual ingredients used in thecompounding of thermosplastic polymers can be employed. Such addedmaterials can include tfillers, antioxidants, light stabilizers, heatstabilizers, plasticizers, etc.

The novel thermoplastic compositions of this invention have improvedphysical properties which are at least similar to the physicalproperties of the major component of the composition. A most strikingaspect of the invention is that additions of cyclic ester polymers inamounts over a wide range are readily accepted by a Wide range ofdiverse thermoplastic polymers and at the same time retain the essentialcharacteristic of the thermoplastic polymer.

In a preferred embodiment, the invention relates to novel shaped andmolded articles, especially fibers, yarns, woven cloth, carpets, etc.,which are formed from novel blends of normally solid, thermoplasticpolyamides such as the nylons illustrated previously and the cyclicester polymers. Such novel shaped and molded articles exhibitoutstanding characteristics such as excellent resistance to soiling andapparent soiling, good anti-static and non-cling properties, significantincrease in opacity (without the addition of titanium dioxide),favorable optical properties especially under artificial lighting,brighter yarn, etc. This significant improvement in characteristics isobtained While maintaining a desirable combination of other mechanicaland physical properties in the novel shaped article.

In this preferred embodiment, the novel blends or shaped articlescomprise cyclic ester polymers which contain from 100 to about 5 molpercent of Units I supra and from 0 to about 95 mol percent of Units 11supra in the polymeric chains thereof, desirably from about 70 to aboutmol percent of Units I and from about 30 to about 90 mol percent ofUnits H, and preferably from about 60 to about mol percent of Units Iand from about 4-0 to about 85 mol percent of Units H. Other moieties orgroups can be interspersed in the polymeric chains of the cyclic esterssuch as the urethane group,

the monoand polyaromatic rings including fused and bridged rings such asphenylene, biphenylene, naphthylene, phenylene-alkylene-phenylene, andphenylene-alkylidenephenylene; initiator moieties; catalyst residues;etc. Such groups, if present, represent a small mol percent of thecyclic ester polymer. Such novel blends or shaped articles can containup to about 15 weight percent, and higher, of cyclic ester polymer,based on the total weight of polyarnide and cyclic ester polymer. Aconcentration of from about one to about 10 weight percent (andpreferably from about 2 to about 7 weight percent) cyclic ester polymerin the novel blend is generally sufficient to obtain novel shaped ormolded articles which exhibit the outstanding properties notedpreviously.

12 DESCRIPTION OF SPECIFIC EMBODIMENTS The following examples arepresented. Unless otherwise specified, all percentages and parts are byweight, all temperatures are on the centigrade scale, and all reducedviscosities are measured at a concentration of 0.2 gram of polymer inmilliliters of benzene at about 30 C. Figures given for physicalproperties in the tables below are averages of test results on two ormore samples of each material and, in some instances, such averages havebeen rounded off.

The testing for various physical properties was done on an Instrontensile tester using specimens about inch wide, 0.020 to 0.30 inch thickand about one inch in gauge length. Gauge length is the length of thespecimen between the jaws of the testing apparatus. The secant modulusor stiffness was determined at a strain rate of 10% in inches per inchper minute and the other tensile property at a strain rate of 100% ininches per inch per minute.

Secant modulus or stitfness This value was determined by subjecting thespecimen to tensile stress and elongating it 1%. The modulus is thencalculated as the ratio of the tensile stress (T) needed to elongate thesample 1% of its original length to the elongation (or strain) of thespecimen.

1% Secant Modulus for 1 in. specimen=T/0.01 =10OT Yield stress Thisvalue was determined as the stress at the first major break in thestress-strain curve and usually corresponds to the necking-in point.

Tensile strength or ultimate strength This value was determined as thetensile stress at rupture of the specimen. It was calculated from theload on the specimen at rupture, divided by the original cross sectionalarea.

Elongation This value was determined as the extension of the specimen atthe point of break or rupture.

Percent elongation X 100 L=length at rupture L =initial length ofspecimen.

Rupture energy This value was determined as the area under the entirestress-strain curve when the sample is subjected to tensile stress up tothe rupture point.

Strain rate Body voltage This involves measurement of the voltage builtup on a person when walking on a carpet. The test is carried outaccording to the revised procedure established by the American CarpetInstitutes Subcommittee on static electricity Aug. 13, 1968 and approvedby the American Carpet Institutes Technical Committee Aug. 19, 1968.

Volume resistivity Current flow is measured through a cm. length oflubricant-free yarn, of approximately 10000 total denier, with 1000volts applied.

Volume resistivity=% ohm ems.

A=Cross sectional polymer area cm. L=length (10 cm.) V=applied voltage(1000) I=current (amperes) Opacity Opacity is a comparative evaluationof individual fibers viewed against a black background under a low powermicroscope.

Lustre This is a subjective evaluation of the relative light refiectancelevel of yarn samples. Fiber containing the cyclic ester polymer to beevaluated may be knitted into a test stocking or, alternatively, it maybe crimped, then tufted into a test carpet for observing lustre.

Relative viscosity This is the ratio of the viscosity of a 1 weightpercent solution of the polymer (or fiber) in sulfuric acid, to that ofthe viscosity of the pure solvent. Viscosities are measured at C. usingan Ostwald capillary viscometer.

Soiling Fiber to be evaluated is either knitted into a test stocking orcrimped and tufted into a test carpet. In this test, 5 inch squaresamples are fastened on the inner wall of a cylinder which rotates aboutits axis, containing standard soiling material and ball bearings. Aftertreatment, the degree of soiling may be rated visually, before or aftervacuuming. Equipment used is a Cyanamid Soil Tester (Custom ScientificInstruments Inc. Model CS-79-012) Heat stability Yarn samples are placedin an oven at 130 C. for 1 hour. Yarn tenacity (grams/ denier), yarnelongation to the break (percent) and yarn color are determined beforeand after the oven exposure. Loss in tenacity or elongation ordevelopment of yellowness indicate the degree of instability to heat.

Light stability and fastness Yarn samples, wound on a black card, areevaluated for tenacity and elongation before and after exposure to Xenonarc light, using a glass filter, in an Atlas Electric Devices Co.Weatherometer Model 600-W-R. Loss in tenacity or elongation over a250-hour exposure period indicates the degree of light instability.

Color fastness is determined by exposing, in the foregoing equipment,dyed samples of test stockings of the zfiber. Color change due to lightexposure is judged by comparing exposed and unexposed portions of thesame dyed stocking.

Extractables Yarn (10 grams) are extracted with methanol in a soxhletapparatus for 8 hours. The methanol is then evaporated, the weight ofthe residue representing the extractables which is expressed as apercentage of the original yarn weight.

EXAMPLE 1 A series of three blends (Nos. 2, 3 and 4) were made by firstfiuxing an aromatic poly(hydroxy ether) made by the reaction ofbisphenol A and epichlorhydrin and having recurring units of theformula:

OCHgCHCHz0 IQ in J 14 The poly(hydroxy ether) had a molecular weight ofabout 30,000, a heat distortion temperature (ASTM D648) of 188 F. at 264p.s.i. and a specific gravity of about 1.182. The poly (hydroxy ether)in each case was fluxed on a tworoll mill at a temperature asrespectively shown in Table I below.

Then, a cyclic ester polymer of epsilon-caprolactone was added to eachfluxing poly(hydroxy ether) in the proportions respectively set forth inTable I. The cyclic ester polymer (PCL) used in each case was preparedby dispersion polymerization in heptane of epsilon-caprolactone in thepresence of 3% vinyl chloride-lauryl methacrylate copolymer asinterfacial agent and 0.1% of triisobutylaluminum as catalyst(percentages based on weight of caprolactone) and had a reducedviscosity of 1.89. After addition of the cyclic ester polymer theresulting blends were milled at the temperatures for the timesrespectively given in Table I and were sheeted off the mill and cooled.During milling of all of the blends, fluxing and banding were observedto be good and all exhibited quite acceptable bank behavior. Also, theremaining milling characteristics were acceptable at the propertemperature.

A similar quantity of the poly(hydroxy ether) identitied above Wasfluxed in the same manner at the temperature listed in Table I for thetime similarly listed. No P-CL was added to this control sample (No. l)which was sheeted oil the mill after the designated milling time.

The resulting blends and control sample were then compression molded at1500 to 2000 p.s.i. and 150 C. for 10 seconds into plaques about 20 to30 mils thick. The plaques were then aged for about 8 days and thenmeasured for physical properties, the results of which are given inTable I. The physical properties were measured again after 22 days agingat ambient temperatures and the obtained values were in agreement withthe respective values given in Table I.

TABLE I Wt. percent PCL 0 1 10 50 1% seeant modulus, p.s.i. 166,000168,000 210,000 Yield stress, p si 9,200 8,900 Tensile strength, p s8,300 7, 500 400 Elongation, percent 280 280 1,300 Rupture energy,in.-lbs./ 19,600 17,400 2,700 Izod impact strength, ft.lbs./i 2. 06 1.92 1. 01 Heat distortion temperature, Q 87 66 Strain rate, in./in./min100 100 100 Milling temperature, C 125 -130 120-140 80130 Milling time,min 5 10 10 e 1% secant modulus values obtained at 10% strain rate,in./in./min. b ASTM 0256-56. a ASTM D64856.

This example illustrates the surprising property of the PCL to blendwell with the poly(hydroxy ether). Visual observations of the 1 and 10%PCL (Nos. 2 and 3) indicated that these blends had better opticalproperties than the poly(hydroxy ether) alone with no PCL added (No. 1).This example also illustrates the flexibilization of poly (hydroxyether) by the addition of PCL to provide a more flexible and toughermaterial. Sample 2, the 50% blend (No. 4), exhibited very good adhesionto aluminum foil. All blends (Nos. 2, 3 and 4) were uniform throughoutand were more flexible than the control sample (No. 1).

EXAMPLE 2 A series of two blends (Nos. 6 and 7) were made by firstfluxing in a Brabender head a cyclic ester polymer and a polysulfonemade by polymerizing bisphenol A and di(parachlorophenyl) sulfone andhaving recurring units of the formula:

CH; O O L a... l J

The polysulfone had a melt flow at 350 C. of about 7.0 dg./min. at 44p.s.i. (ASTM D792), a softening point (ASTM D648) of about 345 F. at 264p.s.i. as deter- 15 mined by heat deflection temperature and a specificgravity of about 1.24. The cyclic ester polymer was made fromepsilon-caprolactone in the same manner as described in Example 1 andwas used in the amounts shown in Table II below. The respective blendswere fluxed for about 5 minutes at a temperature of 250 C. for blend No.6 and a temperature of 230 C. for blend No. 7, using a 190 C. jackettemperature, 125 rpm. rotor speed, and a No. 6 roller head.

Each blend was then compression molded into plaques having a thicknessof about 20 to 30 mils. In addition,

TABLE III Wt. percent PCL- 50 90 1% secant modulus, p 171, 000 150, 000167, 000 164, 000 140, 000 62, 500 39, 000 Yield stress, p s i. 8, 5008, 000 9, 20 8, 300 7, 405) 950 Tensile strength, 1) s 1- 8, 700 8, 7007, 400 5, 900 8, 100 3, 800 4, 500 Elongation, percent 220 63 45 270 4701, 490 Rupture energy, IIL-lbS-llIl- 16, 200 16, 400 3, 800 2, 700 15,200 14, 400 36, 700 Strain rate, in./in./n1in 100 l 100 100 100 l 100 11% secant modulus values obtained at 10% strain rate, in./in./min.

EXAMPLE 4 control plaque (No. 5) of the same approximate thick ness werecompression molded from pellets of the aboveidentified polysulfone. Allplaques were then tested on an Instron tensile tester for physicalproperties and the results are respectively set forth in Table 11.

TABLE II Wt. percent PCL 1% secant modulus, p.

1 1% secant modulus value obtained at 10% strain rate, in./in./min:

EXAMPLE 3 A series of six blends (Nos. 9-14) were made by fiuxing in aBrabender head a cyclic ester polymer and a polycarbonate made by thepolymerization of bisphenol A with phosgene and having recurring unitsof the formula:

The polycarbonate had a high molecular weight, a specific gravity ofabout 1.2 (ASTM D792), a fiexural modulus of 340,000 p.s.i. (ASTM-695),and a heat distortion temperature of about 270 C. at a load of 264p.s.i. (ASTM-D648). The blends were fluxed and milled in a Brabenderhead at a jacket temperature of 170 to 180 C. and a polymer melttemperature at fluxing of about 220 to about 250 C.

Then cyclic ester polymer was used in the proportions respectively setforth in Table I11 below. The cyclic ester polymer (PCL) used in eachcase was prepared by polymerizing epsilon-caprolactone in the mannerdescribed in Example 1. The blends were milled for about 5 to about 10minutes under the conditions given above and then were sheeted 01'1" themill and cooled. The milling characteristics of all blends were goodwith little or no sticking to the surface of the Brabender head.

A similar quantity of polycarbonate (No. 8) identified above was fluxeglin the same manner at the temperature A series of three blends (Nos. 16,17 and 18) were made by fluxing on a two-roll mill a cylic ester polymerand a predominantly polyoxymethylene polymer containing predominantly,i.e., to 98 mol percent oxymethylene units, CH O, and 2 to 5 mol percentoxyethylene units, -CH CH O, made by copolymerizing trioxane with asmall amount of ethylene oxide. This polyoxymethylene polymer had a meltindex of about 9.0 (gms. in 10 mins), a specific gravity of about 1.410(ASTM 792 601), a flow temperature (ASTM D569-59) of about 345 F., and amelting point of about 325 F. to about 330 F.

The cyclic ester polymer (PCL) used was prepared fromepsilon-caprolactone in the same manner as described in Example 1 andwas used in the proportions respectively set forth in Table IV below.The resulting blends were milled for the times and at the temperatureslisted in Table IV below. The milling behavior for all blends was foundto be good and there was little or no sticking to the rolls of thetwo-roll mill.

A similar quantity of the same polyoxymethylene (No. 15) was milled inthe same manner at a temperature of about 160 C. for about 5 minutes. NoPCL was added to this control sample, which was sheeted off the millafter the designated milling time.

The resulting blends and the control sample were then compression moldedinto plaques about 20 to 30 mils thick. The physical properties of theplaques were measured on an Instron tensile tester and the measurementsare given in Table IV below.

TABLE IV Wt. percent PCL 0 10 50 90 1% secant modulus, p.s.i. 170, 000143, 000 67, 000 33, 000 Yield stress, p.s.i- Tensile strength, p.s.i 7,600 6, 500 3, 600 3, 400 Elongation, percent 28 90 20 1, 200 Ruptureenergy, in.lbs,/in. 1, 940 5, 700 650 25, 000 Strain rate, in./in,/min100 100 100 100 Milling temperature, C- ca. 160 160 160 Milling time,min ca. 5 5 10 10 1% seeant modulus values obtained at 10% strain rate,in./in,/min:

EXAMPLE 5 The cyclic ester polymer was used in adequate proportionsrespectively producing the percentages of PCL set forth in Table Vbelow. The cyclic ester polymer (PCL) used in each case was preparedfrom epsilon-caprolactone in the same manner as described in Example 1.The resulting blends were milled for about minutes each at a temperatureof 90 to 100 C. The milling characteristics of all blends were found tobe good.

A similar quantity of the polyoxyethylene polymer identified above wasfiuxed and milled in the same manner as described above, at the sameapproximate temperature and for the same approximate period of time. NoPCL was added to this control sample (No. 19) which was sheeted oft" themill after the designated milling time.

A similar quantity of the cyclic ester polymer identified above wasfluxed in the same manner at the same temperature and for the sameperiod of time as listed above. This control sample (No. 28) containedno polyoxyethylene and was sheeted off the mill after the designatedlength of time.

The resulting blends and control samples were then compression moldedinto plaques about 20 to 30 mils thick. The plaques were then tested forphysical properties on an Instron tensile tester and the measurementsare given in Table V below.

specimen was installed in the tester and locked in position at the marksmade on them. The thickness of each specimen was 10 to 15 mils. Thetester was then closed which stretched the film approximately 5%. Thisamount of stretch was maintained until the film broke. Four to sixspecimens were used in each group. The results are given below:

0% PCLAll specimens broke after 3 to 5 minutes.

1% PCLA11 specimens did not break for 14 to 21 minutes.

2% PCLAll specimens did not break for 20 to minutes.

5% PCL-All specimens did not break for 1 to 2 hours. One specimen didnot break but only necked when stretched for approximately 40 hours.

10% PCL-All specimens did not break for minutes to 45 minutes. Onespecimen did not break for 72 hours. One specimen only slightly neckedwhen stretched for about 192 hours.

20% PCL-All specimens didnot break for 30 minutes to 5 hours. Onespecimen did not break but only slightly necked when stretchedapproximately 20 hours.

This test illustrates the toughness or stress endurance imparted by PCLto the polyoxyethylene.

TABLE V Percent PCL 0 2 5 10 50 75 90 100 Rupture energy, in.-lbs./in.5,165 17,802 15, 421 29, 235 24, 932 29, 953 as, 281 37,536 46, 94671,887 Elongation, percent. 370 1, 468 1, 269 2, 254 1,811 1, 958 1, 8331, 549 1, 729 1, 930 Tensile strength, p s 1 1, 229 1, 247 1, 110 1, 3831, 500 1, 930 3,557 4, 217 6, 219 7,078 Yield stress, p.S.i 1, 790 1, 541, 631 1, 464 1, 640 1, 654 1,825 1, 581 1, 589 1, 674 Secant modulus,dynes/cm a34 10 a 25x10 a32 10 a34 10 as7 10 2 95x10 321x10 215x10 164x10 1. 85x10 Strain rate 100 1 100 100 100 100 100 100 100 These dataillustrate the improvement in physical prop- EXAMPLE 6 erties of theblends over polyoxyethylene alone.

The blends and the control sample containing no PCL were then tested ina series of swelling studies. In these tests, a plaque of each blend andthe control sample measuring about one inch by one-quarter inch wasplaced in a test tube with 3 cc. of distilled water and allowed to soakwhile being observed. The results are listed below.

0% PCL-deformed in 5 minutes, disintegrated in 65 minutes, andcompletely dissolved in 3 hours.

1% PCLdeformed in 5 minutes, disintegrated in 65 minutes, but did notcompletely dissolve.

2% PCL-deformed in 5 minutes, disintegrated in 65 minutes, but did notcompletely dissolve.

5% PCLdeformed in 5 minutes, disintegrated in 65 minutes, but did notcompletely dissolve.

10% PCL-deformed in 5 minutes, disintegrated in 24 hours, but did notcompletely dissolve.

20% PCLslightly deformed in 17 minutes, did not disintegrate ordissolve.

50% PCLno visible change during or after a 24-hour soaking period.

75% PCL-no visible change during or after a 24-hour soaking period.

90% PCLno visible change during or after a 24-hour soaking period.

The percent weight losses for the 20% -PCL, 50% PCL and 75% PCL blendsafter the above-described soaking and then drying for 29 hours in vacuumat room temperature were measured and were found to be, respectively, 74weight percent, 45 weight percent and 12 weight percent. This testillustrates the waterproofness imparted to polyoxyethylene by thepresence of PCL. In addition, it illustrates that the polyoxyethylenepolymer may be leached from the blend leaving a porous or microporousmatrix, which is largely PCL.

The blends containing 1%, 2%, 5%, 10% and 20% PCL and the control samplecontaining no PCL were tested in a stress endurance testing device. Thetest specimens were cut 7% inches long and A inch wide. Marks were madeon each specimen 5 inches apart and each A series of three blends (Nos.29-31) were made from a cyclic ester polymer and a maleicanhydride-methyl vinyl ether copolymer of medium molecular weight havinga softening point range of about 200 to 225 C., a specific viscosity of1.0 to 1.4 dl./g. at a concentration of l g. copolymer dissolved in ml.methyl ethyl ketone at 25 C. and a specific gravity as a film of 1.37.

The cyclic ester polymer (PCL) used in each case was prepared in thesame manner as described in Example 1 and the amount used Was sufiicientto provide the percentages listed in Table VI below.

In making the 10% PCL blend, the copolymer was added to the mill firstand then the PCL but milling behavior was poor to fair in most respectsalthough it was good respecting bank and hot strength. Therefore, inmaking the 50% PCL and 90% PCL blends, the PCL was first added to themill and then the copolymer and milling behavior was very much improvedin all respects. The resulting blends were milled on a two-roll mill forabout 5 minutes at to C. The blends were then compression molded intoplaques about 20 to 30 mils thick.

Attempts were made to compression mold the control sample of thecopolymer containing no PCL. However, gas coming off of the sampleduring heating forced the molding plates apart and prevented moldingeven under a pressure of 20,000 p.s.i. at a temperature of 215 C. for 2minutes. The control sample shrank and turned brown in the attempts tocompression mold it.

The plaques formed from the blends were tested in an Instron tensiletester and the physical properties are given in Table VI below.

No'rE.Data obtained at 100% strain rate.

19 This example illustrates the modification of a difiicultly moldablepolymer in accordance with this invention to render it more easilymoldable.

EXAMPLE 7 A series of three, blends were made by fluxing on a two-rollmill a cyclic ester polymer and a high purity cellulose tridecanoatehaving all three hydroxyl hydrogens of each anhydroglucose unitsubstituted with decanoyl groups and a glass transition temperature ofabout 60 C. determined from mechanical loss measurements made with arecording torsion pendulum that operated at about one cyclic per second.Cellulose tridecanoate of this type has a melting point range of about85 to about 95 C., a density of about 1.015 to about 1.02 g./ml., and aspecific rotation in chloroform with 589 millimicron light at 25 C. ofabout 2 C.

The cyclic ester polymer was used in sufficient amounts to provide theproportions respectively set forth in Table VII below. The cyclic esterpolymer (PCL) used in each case was prepared from epsilon-caprolactonein the same manner as described in Example 1. The resulting blends weremilled at a temperature of about 50 to about 90 C. for approximately 5minutes, and then sheeted oif of the mill and cooled. Milling behaviorfor all blends was quite good.

A similar quantity of the cellulose tridecanoate identified above wasfiuxed in the same manner at a temperature of about 90 C. for about 5minutes. No PCL was added to this control sample.

The resulting blends and control sample were then compression moldedinto plaques about to mils thick. The plaques were then tested in anInstron tensile Leslted and the physical properties are given in TableVII e ow.

N o'rE.-Data obtained at 100% strain rate.

All samples were compression molded at 80 to 110 C. for 10 seconds at500 p.s.i. The milling behavior as well as most physical properties ofthe blends improved as the amount of PCL in the blends was increased.

EXAMPLE 8 Two blends were made by mixing the granulated forms of cyclicester polymer (PCL) of epsilon-caprolactone (same as used in Example 1)and nylon 6 in amounts adequate to provide the percentages of PCL listedin Table VIII below. The nylon used was Firestone Nylon 6 Type 200001.Melt indices at various temperatures were found to be as follows:

ps Melt index 260 23.5 2 35.2 280 50.5 290 64.0 300 82.8 310 86.5

The powder blend was heated to melt the powder while under a nitrogenatmosphere and stirred until the blend 20 was thoroughly mixed anduniform. The blend was then cooled to room temperature under a nitrogenatmosphere. Plaques about 20 to 30 mils thick were compression moldedfrom each blend and these plaques were tested in an Instron tensiletester. The physical properties are given below:

N orrL-Data obtained at strain rate.

EXAMPLE 9 Three blends were prepared each containing 400 parts of nylon6 pellets containing titanium dioxide and, respectively, 10.29 parts,21.05 parts, and 44.45 parts of a cyclic ester polymer (PCL) ofepsilon-caprolactone prepared in the same manner as described in Example1, except 0.3% catalyst was used and the resulting cyclic ester polymerhad a reduced viscosity of 1.98. Nylon 6 of this type was purchased fromCourtaulds as Dull 704, contains T iO and has a relative viscositywithout the TiO' of 2.26 in sulfuric acid at 1% nylon concentration. Theblends were prepared by dissolving the cyclic ester polymer in 400 partsof methylene chloride. Each of the resulting solutions was thencontacted with the nylon pellets and the resulting mixture was thenstirred and dried to effect a substantial coating of the nylon with thecyclic ester polymer.

A control sample of the same nylon 6 was treated with an equivalentamount of methylene chloride which contained no PCL.

These blends and control sample were then mixed with an equal weight ofthe same nylon 6 but which had not been treated with MeCl or PCL. Thusthe final blends contained 1.25%, 2.5% and 5% PCL. Each of the blendsand control sample were then spun into multifilament yarns using aspinning head temperature of 265 C. and a polymer temperature of 245 C.The spinneret had 25 holes of 0.020 in. diameter. The measured yarntake-up velocity was 300 feet per minute and the orifice velocity was 5-feet per minute giving a melt-draw ratio of 60 to 1. Spinning behaviorwas good with the 0%, 1.25% and 2.5% PCL blends. The cold-drawing orstretch data are given in Table IX. The stretching aid in thecold-drawing process was a C. pin. The physical properties of these spunyarns are listed in Table D(.

TAB LE IX Percent PCL 0 1. 25 2. 5 5

Cold draw data:

Feed rate, ft./m.in 100 100 100 100 Take-up rate, f ./min 480 500 480420 Percent stretch 380 400 380 320 Average denier 178 171 179 207Tenacity gm./dem 7. 2 6. 9 6. 2 5. 0 Percent elongation 15. 2 15. 4 16.9 18. 9 Stifiness gm./denier 43. 6 44. 0 37. 0 31. 6

The spun fibers were dyed with:

(1) Celliton Fast Navy Blue BA, a disperse dyestutf (2) Celliton FastRed GGA, a disperse dyestuif 22 The blends as well as a control samplecontaining no PCL were compression molded under a pressure of 5000p.s.i. for the control sample and the 1% blend and 1000 p.s.i. for theremaining blends. The compression molding temperature was 170 to 190 C.and molding time Celliton Fast Black B'A a dis ers d e tutf 8; Ca ac 1Red B a enletaniid g was 10 seconds. Each of the resulting plaques,about Pr Y Pr y u to 30 mils thick, was then tested in an Instrontensile All lf had excellent l P however the tester and the physicalproperties are listed in Table XI PCL containing blends had slightlydeeper colors. b l

TABLE XI P tPOL Riiiiire energy, in.-lbs./in.' 28g 12; 7 438 Elongation,percent. 6 4 3 3 '473 sil Strength, rm. 5, 93s 5, 262 2, 884 1, 667 1,628 Yield stress, p.s.i-.. 1, 642 Secant modulus, dynes/cmfl--- 12 1o 1347x10 9. 75x10 4.9x10' 2. 58x10 Norm-Data obtained at 100% strain rate.

EXAMPLE 10 EXAMPLE 12 A series of three blends were made by fiuxing on atwo-roll mill a cyclic ester polymer and a stilbene-acrylonitrilecopolymer.

The acrylonitrile-stilbene copolymer was prepared by solutionpolymerization in dimethyl formamide. The copolymer composition bymonomer charge was 33/67 acrylonitrile-stilbene on a weight basis.Nitrogen analysis showed that composition obtained was 49.7/51.3acrylonitrile-stilbene on a weight basis. The catalysts used were 0.5%dibenzoylperoxide and 0.5 azobis[isobutyronitrile]. Reduced viscosity ofthe copolymer in dimethylformamide at C. was 0.36 dl./ gm. when measuredat a concentration of 0.2 gm./100 ml. The cyclic ester polymer (PCL) wasmade from epsilon-caprolactone in the manner described in Example 1 andwas used in amounts adequate to provide the proportions of PCLrespectively set forth in Table X below. The resulting blends weremilled for 5- minutes at about 175 C. During milling, it was noted thatfluxing, dispersion and banding were quite good. After the designatedmilling time, the blends were sheeted 01f of the mill and cooled.Plaques were compression molded from each of the milled blends and thetensile properties were determined with an Instron tensile tester. Thetensile properties are given in the table below.

TABLE X Percent PCL 25 90 5O Rupture energy, in.-lbs [1n 1 5 53 5,082Elongation, percent. 1 4 325 Tensile strength, p.s.i. 1, 116 2, 170 1,635 Yield stress, p.s.i 1, 916 Secant modulus, dyness/cm. 9. l1 10 5.9x10 2 89 10 No'rE.Data obtained at 100% strain rate.

EXAMPLE 11 A series of four blends were made by fiuxing on a tworollmill a cyclic ester polymer and an acetylated ethyl cellulose having anMS. of 1.1 (an average of 1.1 mols of ethylene oxide chemically added toeach anhydroglucose unit), a D8. of 1.6 (an average of 1.6 acetyl groupssubstituted for hydroxyl hydrogen per anhydroglucose unit) and having areduced viscosity of 3.62 d1./g. at a concentration of 0.2 g. acetylatedethyl cellulose dissolved in 100 ml. dimethylsulfoxide at 30 C.

The cyclic ester polymer was used in amounts adequate to provide theproportions listed in Table XI below. The cyclic ester polymer (PCL)used was made from epsilon-caprolactone in the same manner as describedin Example 1. The resulting blends were milled for about 5 minutes atabout 180 C. and then each blend was sheeted ofi of the mill and cooled.It was noted during milling that those blends containing more PCLprovided better mill behavior. At 10% PCL and more, fluxing, banding,bank and dispersion characteristics were good.

A Ablend was prepared by milling equal parts of carboxymethyl celluloseand a cyclic ester polymer of epsilon-caprolactone made in the samemanner as described in Example 1. The carboxymethyl cellulose had adegree of polymerization of about 3000 and an average degree ofcarboxymethylation of about 0.8 to 1.0. The two materials were milledtogether at 70 C. and sheeted off of a mill and cooled. The resultingfilm had a substantial flexibility quite unlike carboxymethyl cellulosealone and was tough and leathery. The blend could be molded attemperatures of about C. to C.

EXAMPLE 13 A series of four blends (Nos. 52-55) were made from cellulosetriacetate and a cyclic ester polymer, PCL. The cyclic ester polymerused was prepared by the bulk polymerization of epsilon-caprolactoneusing 0.2 weight percent stannous octoate as catalyst. This substantialhomopolymer had a reduced viscosity of 0.65 dl./gm.

Arnel cellulose triacetate fibers (Celanese, 200 denier, filament 52, SHLuster, type bright) were used as the cellulose triacetate. This type offiber has a melting range at about 572 F., a specific gravity of about1.3 and is further described in Textile World, 1962, Man-Made FiberChart. The fibers were washed twice with isopropanol to scour them oflusterants and other materials and then dried in a vacuum oven to removeexcess or residual isopropanol.

Solutions of the blends of scoured fibers and the PCL, and a controlsolution of the scoured fibers (No. 51) containing no PCL, were preparedin methylene chloride in the weight ratios indicated in Table XII. Thesolutions were warmed slightly to effect solution. Thin films were thencast onto Teflon and dried for about one hour or more. Portions of thethin films were tested in an Instron tensile tester to determine tensileproperties. Results are shown in Table XII.

The film clarity given in Table XII was judged by visual observation.There is a definte increase in haze as the PCL content is increased. Allfilms are very smooth except for the 30% PCL film which is rough. The30% PCL film absorbed fountain pen ink and, after dry, writings on itcould not be easily rubbed 01f. They could be easily rubbed ofi of theother films. The haze increase in the blends with increasing PCL permitsthe manufacture of a more opaque fiber, i.e. one which has a greaterhiding capacity. In addition, the tensile properties of the 10%, 20% and25% PCL-containing blends show that PCL is acting as a polymericplasticizer for the cellulose triacetate permitting a tougher fiber whenblends of the two materials are spun into a fiber.

TABLE XII Parts CL 1 2 5 6 Cellulose trlaceta 9 9 8 14 MeC 90 90 90 9090 Percent PCL 0 10 1% secant modulus, p s 210, 000 208, 000 166, 000151, 000 153, 000 Tensile strength, p s i 9, 700 9, 100 7, 200 9, 200 5,Elongation, percent" 14 15 22 5 Rupture energy, in.-lbs.lin. 1, 100 1,060 1, 500 1, 780 150 Film clarity 1 Clear.

1 Clear but slightly hazy.

a Clear but somewhat hazy. 4 Clear but quite hazy.

6 Clear but very hazy.

EXAMPLE 14 A series of two blends '(Nos. 57 and 58) were made fromcellulose diacetate and a cyclic ester polymer (PCL) The cyclic esterpolymer was prepared by bulk polymerization of epsilon-caprolactoneusing stannous octoate as catalyst. The substantial homopolymer had areduced viscosity of 0.65 dl./ gm.

The cellulose diacetate used was an Eastman product having an acetylcontent of 40% and an ASTM viscosity of 25.

Solutions of the two blends and a control solution (No. 56) containingcellulose diacetate but no =PCL were prepared in acetone in the weightratios indicated in Table XIH. The solutions were warmed to about 55 C.to aid in effecting solution. Thin [films were then cast on Teflon. Thefilms were covered during drying. When dry, portions of the films weretested in an Instron tensile tester to determine tensile propertieswhich are summarized in Table XIII.

Film clarity was judged by visual observation. All films were smooth.The data show that low amounts of PCL will plasticize cellulosediacetate. The haze development permits a more opaque fiber with greaterhiding power to be spun from such blends.

TABLE XIII Parts:

PO 0 2 4 Cellulose diacetate 18 18 16 Acetone 90 90 90 Percent PCL 0 1020 1% secant modulus, p i 216, 000 146,000 116,000 Tensile strength,p.s.i 13, 700 10, 200 6, 000 Elongation, percent.- 6 18 4 600 1, 300 160Rupture energy, ln.lb Film clarity 1 Clear.

2 Very slight haze. Slight haze.

EXAMPLE 15 A series of five blends (Nos. 60-64) were made from achlorinated polyether and a cyclic ester polymer (PCL).

Penton (Hercules Powder Co., Inc.) was the chlorinated polyether used.Its monomer, which is a chlorinated oxetane, is synthesized frompentaerythritol. The chlorinated polyether had a molecular weightaverage range of 250,000 to 350,000. It is a linear thermoplasticpolymer that is crystalline in nature and has recurring units of theformula:

and plaques were compression molded. Plaques as control samples (No. 59)were also compression molded from the chlorinated polyether whichcontained no PCL. Strips cut from these plaques were used to determinethe tensile properties which are summarized in Table XIV using anInstron tensile tester. The glass transition temperatures, T,;, shown inthe table were taken from the maximum in the loss component of thecomplex shear modulus which was determined through data taken with arecording torsion pendulum. Frequency of measurement at T was about 1 to2 cycles per second.

The results in Table XIV show that "PCL is a polymeric plasticizer forchlorinated polyether. Increasing amounts of PCL produced a tougherproduct.

1 Not milled (Plaque merely molded).

EXAMPLE 16 A series of three blends (Nos. 66-68) were made from athermoplastic poly(epichlorhydrin) and a cyclic ester polymer (PCL)prepared from epsilon-caprolactone in the manner described in Example 1.The poly(epichlorhydrin) used was a commercial product sold by B. F.Goodrich Co. under the name Hydrin 100. It contained recurring units ofthe formula:

- Homo and had a specific gravity of about 1.36. The polymer had areduced viscosity of about 2 dL/gm. when measured in dimethylformamideat 30 C. and a concentration of 0.2 gm./ ml.

Blends of these two polymers and a poly(epichlorhydrin) control samplewith no PCL (No. 65) were milled on a two-roll mill at C. using amilling time of about 5 minutes. Milling behavior: fluxing, banding,bank and dispersion were good for the control sample and for all blends.Roll release and hot strength were poor for the control sample and forthe blends. After hot blending, the blends and control sample wereremoved from the mill and compression molded into plaques.

Physical properties of blends and the control sample were determinedwith an Instron tensile tester. These physical properties are given inTable XV. The properties were determined on strips about inch wide, 1inch long (gauge length) and about 0.030 inch thick. The glasstransition temperatures, T were determined as described in Example 15.

I'CH: Cl

The above test results show that blends containing PCL have improvedcreep resistance, improved moldability and formability, and improved lowtemperature properties. PCL is a polymeric plasticizer for thepolyepichlorohydrin elastomers.

The blends containing 50%, and especially 90%, or more of PCL are usefulas low melt adhesives having improved cohesive strength. Moreover, theblends containing 40% or more PCL are useful in the production of filmswhich can be oriented by stretching at elevated temperatures below themelting point of the blends and cooling while maintaining the stretchedcondition. Such oriented films are useful as heat shrinkable films forpackages, seals, repair tapes or films and connectors.

EXAMPLE 17 A series of three blends (Nos. 70 72) were made from athermoplastic epichlorhydrin-ethylene oxide copolymer and a cyclic esterpolymer (PCL) prepared from epsiloncaprolactone in the same manner asdescribed in Example 1. The epichlorhydrin-ethyleue oxide copolymer usedwas a commercial product, Hydrin 200, sold by B. F. Goodrich Co. Itcontained recurring units of the formulas:

011201 '1 F H 1 -CHCH o and 2 4 L l J L l and had a specific viscosityof 1.27. The polymer had a reduced viscosity of about 3.3 dl./gm. whenmeasured in dimethylformamide at 30 C. and a concentration of 0.2 gm.per 100 ml.

Blends of these two polymers and a copolymer control sample (No. 69)containing no PCL were milled on a two-roll mill at 120 C. using amilling time of 5 minutes. Milling behavior in fluxing, banding anddispersion were good. Bank, roll release and hot strength wereconsiderably improved in the blends as compared to the control sampleand thus the hot processability of the blends was considerably betterthan that of the control sample. After hot blending the control samplesand the blends were compression molded into plaques.

Physical properties of the blends were determined with an Instrontensile tester. These physical properties are given in Table XVI. Theproperties were determined on strips about 4 inch wide, 1 inch long, and0.030 inch thick. The glass transition temperatures, T were determinedas described in Example 15.

TABLE XVI Percent PCL 0 50 90 1% secant modulus, p s i 50 530 7, 700 29,000 Tensile strength, p.s. 80 0 6, 500 Elongation, percent. 230 670 1,500 1,900 Rupture energy, in.-lbs./in. 50 460 22, 400 58,000 49 Theseresults show that addition of PCL improves the creep resistance of thecopolymer, improves moldability and formability of the copolymer, andimproves the low temperature properties of the copolymer.

26 ages, seals, repair tapes or films and connectors. For example, afilm of the 50% PCL blend and a film of the PCL blend were each hotstretch oriented in the above fashion and wrapped around an elongatedobject. The films in each case were warmed to about 50 C. and allowed tocool. The tapes adhered tightly to the object.

EXAMPLE 18 A particulate cyclic ester polymer (PCL) made by dispersionpolymerization of epsilon-caprolactone in the presence of vinylchloride-lauryl methacrylate copolymer as interfacial agent andtriisobutylaluminum as catalyst and having a reduced viscosity of 0.6was mixed in different proportions as shown in Table XVII with celluloseacetate butyrate (Tenth Second butyrate, Eastman Chemi cal Products)containing 13 percent acetal and 37 percent butyral and having aviscosity of about 0.1 second as determined by 'ASTM method D-l343-54T.These mixtures were prepared by dissolving each of the polymers in2-nitropropane to give solutions containing about 20 percent polymer.Admixtures of these solutions were then prepared in the proportionsshown in Table XVII hereinafter. Films of these mixed solutions werecast on glass plates giving dried films about 5 to 6 mils thick. Thetensile properties of the dried films were determined and the resultingdata are given in Table XVII.

TABLE XVII [Physical properties of poly-epsilon-caprolactone/celluloseacetate butyrate] Ultimate tensile Ratio of PCL/cellulose strength,acetate butyrate, pounds/ Percent by weight inch elongation 1 ASTM683-67T.

The films containing less than about 50 percent of PCL were clear,indicating compatibility of PCL and cellulose acetate butyrate in thisrange of compositions. Films with about 50 percent PCL or higher werehazy. Films containing less than about 10 percent PCL were too brittleto be removed intact from the glass plates for testing.

The demonstrated compatibility of PCL with cellulose acetate butyrateindicates the wide scope of applications of cyclic ester polymers asmodifiers for cellulosic polymers. Cellulosic polymers are, of course,used in a wide variety of applications, such as, molded articles,protective coatings, paints, and inks, to mention only a few.

EXAMPLE 19 The cyclic ester polymer (PCL) used was a homopolymerprepared by the dispersion process using heptane as the non-solvent and5% of a vinyl chloride/laurylmethacrylate copolymer as the interfacialagent. Catalyst was 0.6% dibutyl zinc. Reduced viscosity of the PCL was3.17.

The polyurethane used was made from 1 mole polyol, 2 moles MDI and 1mole 1,4-butanediol. The polyol is a 2000 number average molecularweight polycaprolactone diol that is prepared from epsilon-caprolactoneusing diethylene glycol as the initiator and is hydroxy terminated onboth ends. MDI is 4,4'-di-phenylmethane diisocyanate. The polyurethanewas prepared in the following manner. The polyol and 1,4-butane diol aremixed and heated to C. Then the MDI is added and after mixing well (1 or2 min. after the MDI addition) the system is placed in a forced-air ovenset at C. for 1 hour to cure. .After this the system is cooled to roomtemperature and granulated. The result is a thermoplastic polyurethanehaving a reduced viscosity of about 0.8 when measured 27 indimethylformamide at 30 C. and a concentration of 0.2 gm. per 100 ml. 16parts of PCL and 4 parts of the polyurethane were blended on a two-rollmill for 5 minutes at 140 C. Milling behavior was good although therewas some sticking to the mill rolls. After blending the mixture wasremoved from the mill, cooled, and then compression molded into plaquesat 150 C. and 1000 p.s.i. for 10 sec. The physical properties of theblend are compared with those of a control sample of the samepolyurethane containing no PCL in Table XVIII. Approximate specimen sizewas A in. X 1 in. X 0.030 in.

TABLE xvrrr Percent PCL 1% secand modulus, p 25,000

Tensile strength, p.s.i 5, 000 6,000

Pertlagntt elongatitimnn 1, 850 i, r ss .5.

Rupture energy, in.-lbs./in.

The cyclic ester polymer (PCL) used was a blend of four substantialhomopolymers prepared by the dispersion polymerization ofepsilon-caprolactone in heptane using a vinyl chloride/laurylmethacrylate copolymer as the interfacial agent. Three of thesubstantial homopolymers were prepared using triisobutylaluminum as thecatalyst, and one was prepared with dibutylzinc as the catalyst. Theblend had a reduced viscosity of about 1.4 dl./ gm.

The polyurethane used was a thermoplastic elastomer prepared from 1 molepolyol, 1.95 moles MDI, and 1 mole of 1,5-pentanediol. The polyol was a2000 number average molecular weight polycaprolactone diol that wasprepared from epsilon-caprolactone using 1,4-butanedio1 as the initiatorand was hydroxy terminated on both ends. MDI is 4,4-diphenylmethanediisocyanate. The polyurethane was prepared in the following manner.After mixing the polyol and 1,5-pentanediol at about 145 C., the MDI wasadded. After mixing well (1 or 2 minutes after the MDI addition) thesystem was placed in a forced air oven set at 180 C. for one hour topolymerize. After this, the system was cooled to room temperature andgranulated. The result was a thermoplastic polyurethane that had anintrinsic viscosity (i.e. the extrapolation of reduced viscosity valuesto zero concentration) of 0.86 dl./ gm. when measured indimethylformamide at 30 C.

The PCL and polyurethane were blended on a two-roll mill at 140 C. forabout five minutes. The milling behavior was good regarding fluxing,banding, and dispersion. There was some rolling in regard to the bankbehavior. Roll release was poor, and hot strength of blend was fair.Details of blend compositions and physical properties of the blends aregiven in Table I as compared to those of the polyurethane containing noPCL.

TABLE XIX Parts:

Polyurethane 150. 142. 5 135. 0 120. 0 105. 0 PCL 0 7. 5 15.0 30. 0 45.0

Percent PCL 0 5 30 Hardness, Shore A (ASTM D2210-64T) 86 86 90 Hardness,Shore D (ASTM D224064T 46 100% tensile modulus 1 1, 587 1, 507 1, 119 1,311 1, 510 300% tensile modulus 1 2, 578 2, 404 1, 929 1, 843 1, 855Tensile strength 3,148 2, 940 2, 989 3, 253 3, 433 Ultimate elongation 1477 455 530 608 645 Tear resistance, die C (ASTM D624'54) 728 678 598670 676 Compression Set, B (ASTM D395-61, Method B, 22 hrs. at

158 F. 62 63 60 64 60 Rebound resilience, percent (Zwick dz 00., ModelZ51E rebound pendulum) 34 37 34 36 39 l ASTM DMZ-66.

These data indicate that a more extensible and a softer (as shown bytensile modulus) material is made when PCL is blended with thepolyurethane without major changes in hardness, tensile strength, tear,compression set, or resilience.

Substantially similar results are obtained as in respectively Examples1-19 when the substantial homopolymers of, and copolymers of two or moreof, the following cyclic esters are respectively substituted for theepsiloncaprolactone polymer in each of these examples:deltavalerolactone, zeta-enantholactone, eta-caprylolactone,monomethyl-delta-valerol-lactone, monohexyl-delta-valerolactone, tri npropyl-epsilon caprolactone, monomethoxy delta valerolactone,diethoxy-delta-valerolactone, diethyl-epsilon-caprolactone andmonoisopropoxy-epsiloncaprolactone.

EXAMPLE 21 To a reaction vessel containing 1000 grams of apolyoxyethylene glycol having an average molecular weight ofapproximately 6000 heated to about 65 C. in a nitrogen atmosphere, therewere added 8.87 grams of aqueous 50 percent sodium hydroxide solution.The resulting admixture was stirred until solution resulted. Thereaftera 109 gram portion of this solution was transferred to anothe vessel andheated to C. in a nitrogen atmosphere, and 2.88 grams of diglycidylether of 2,2-bis(4-hydroxyphenyl)propane were quickly added, withstirring. This amount corresponds to a molar ratio of 0.5 :1 of thediglycidyl ether to the polyoxyethylene glycol. Thereafter thetemperature was held within the range of 95 C. to 110 C. for 40 minutes,and the reaction mixture was allowed to cool to room temperature andsolidify. The solid material was a tan-colored wax which melted at 60 C.This dihydroxyl-terminated product was characterized by a polymericchain having three polyoxyethylene segments therein which averaged about6,000 molecular weight each, said chain being interspersed with the twophenylene-propylidene-phenylene moieties from the di glycidyl dietherreactant.

EXAMPLE 22 Three hundred grams of epsilon-caprolactone and three hundredgrams of the hydroxyl-terrninated polyether compound of Example 21 suprawere added to a 1000 milliliter, 4-neck flask, equipped with athemometer and stirrer. The system was sparged with nitrogen, heated toC., and again sparged for about an hour with nitrogen. Thereafter 0.3gram of stannous dioctanoate was added and the resulting reactionmixtures heated to C. and held at this temperature for 10 hours. Duringthe entire period, the reaction mixture was maintained under nitrogen.When cooled to room temperature, there was obtained an opaque, whitecrystalline (polymeric product. Thereafter, this polymeric product washeated to 180 C. and held at this temperature for one hour under vacuum,e.g., about 1 mm. of Hg. The polymeric product was then cooled to roomtempearture dissolved in benzene, and precipitated and washed withhexane. There was obtained 575 grams of a fine White powdery blockpolymer having an ABA configuration in which the A blocks are recurringoxypentamethylenecarbonyl units and the B block represents the productof Example 21 (without the terminal hydroxylic hydrogen atoms). To testwater solubility, 6.6 of this ABA block polymeric product was placed in70.2 grams of distilled water and stirred overnight. After settling analiquot of the supernatant liquid, i.e., 6.9 grams, was removed anddried to constant weight. The residue weighed 0.027 gram indicating thatvirtually no part of the block polymeric product was water solublereconfirming that the desired reaction had taken place.

EXAMPLE 23 Three hundred grams of epsilon-caprolactone and three hundredgrams of polyoxyethylene glycol having an average molecular weight ofabout 6,000 were added to a 1000-milliliter, 4-neck flask, equipped witha thermometer and stirrer. The system was sparged with nitrogen, heatedto 115 C., and again sparged for about an hour with nitrogen. Thereafter0.25 gram of stannous dioctanoate was added and the resulting reactionmixture heated to 180 C. and held at this temperature for hours. Duringthe entire period, the reaction mixture was maintained under nitrogen.When cooled to room temperautre, there was obtained an opaque, whitecrystalline, polymeric product. Thereafter, this polymeric product washeated to 180 C. and held at this temperature for one hour under vacuum,e.g., about 1 mm. of Hg. The polymeric product was cooled to roomtemperature, dissolved in benzene, and precipitated and washed withhexane. There was obtained a solid white block polymer having an ABAconfiguration in which the A blocks are recurringoxypentamethylenecarbonyl units and in which the B block representsrecurring oxyethylene units.

EXAMPLE 24 Epsilon-caprolactone (1000 parts by weight) andpolyoxyethylene glycol having an average molecular weight of about 3000(300 parts by weight) were added to a reaction vessel. Stannousdioctanoate (1.0 part by Weight) was added thereto. The vessel then wasplaced in an oil bath maintained at 180 C. for a period of 24 hours.Upon cooling to room temperature the resulting reaction product mixturewas dissolved in benzene, followed by precipitation and washing withhexane, and then dried in a vacuum oven at room temperature for 3 days.There was obtained a water-insoluble, white, solid block polymer havingan ABA configuration in which the A blocks are recurringoxypentamethylenecarbonyl units and in which the B block representsrecurring oxyethylene units.

EXAMPLE 25 In a manner similar to Example 24 supra, whenmethyl-epsilon-caprolactone is used in lieu of epsilon-caprolactone,there is obtained a water-insoluble, white, solid block polymer.

EXAM PLE 2'6 Epsilon-caprolactone (100 parts by weight) and themonomethyl ether of polyoxyethylene glycol having an average molecularWeight of about 4000 (80 parts by weight) were added to a reactionvessel which was sparged with nitrogen, heated to 120 C., and againsparged for about an hour with nitrogen. Thereafter 0.2 part by weightof stannous dioctanoate was added and the resulting reaction mixture washeated to 180 C. under nitrogen and held at this temperautre for 8hours. When cooled to room temperature, there was obtained awater-insoluble, white solid block polymeric product having an ABconfiguration in which the A block represents recurringoxypentamethylenecarbonyl units and in which the -B block representsrecurring oxyethylene units.

EXAMPLES 27-32 Five blends of nylon 6 and the cyclic ester polymerprepared in the manner set out in Example 22 were spun intomultifilament yarns according to the procedure indicated previously. Thevolume resistivity and opacity of carpets made from such yarns were thendetermined and compared with a control which contained no cyclic esterpolymer. The results are set out in Table XX.

TABLE XX Cyclic ester polymer, 5 wt. Volume resistivity Example numberpercent 1 (ohm-cm.) Opacity 2. 2X10" 6 1. 2X10- 1. 5X10- 3. 8Xl0- 3 5.6X10 2 8. 3X10 1 1 Cyclic ester polymer is an ABA block polymer preparedaccording to the procedure set out in Example 22.

2 ABA block polymer in which the A blocks represent wt. percentrecurrilfg oxypentamethycarbony lunits and in which the B blockrepresents about 20 wt. percent recurring oxyethylene units prepared asnoted in Example 21:

3 Same as footnote 2 except that the A blocks represent 50 wt. percentand the B block represents 50 wt. percent.

4 Same as footnote 2 except that the A blocks represent 55 wt. percentand the B block represents 46 wt. percent.

5 ABA block polymer; B block derived from polyethylene glycol 6,000. Ablocks represent 33 wt. percent oxypentamethylencarbonyl units and Bblock represents 67 wt. percent oxyethylene units.

Same as footnote 6 except that A blocks represent 30 wt. percent and theB block represents 70 wt. percent.

An opacity value of 1 is the most opaque; blend has no TiOz.

EXAMPLES 3 3-34 A blend of nylon 6 and the cyclic ester polymer preparedin the manner set out in Example 23 were spun into multifilament yarns.Samples of carpet were woven from such yarns. The results of soil testswere determined and compared with a control (no cyclic ester in theblend). The results are set out in Table XXI below.

TABLE XXI Cyclic After ester 20-minute vacuum polymer, cycle withcleaning Example 5 wt. 0.02 gram After vacuum and number percent soilcleaning shampooing 33 Contro1 Heavy s0iling Slight Very slightimprovesoiling ment. remaining. 34 Light soiling ..do Restored tooriginal condition.

1 ABA block polymer prepared according to the procedure set out inExample 23 using polyethylene glycol 6,000. A blocks represent 30 wt.percent oxypentarnethylene units and B block represents 70 wt. percentoxyethylene units.

What is claimed is:

1. A thermoplastic composition consisting essentially of a blend about 1to about weight percent of a cyclic ester polymer having a reducedviscosity of about 0.1 to about 15 and containing at least a major molaramount of recurring Units I of the formula:

3, and up to a minor molar amount of recurring Units 11 of the formula:

wherein each R is selected from the class consisting of, individually,hydrogen, alkyl, cycloalkyl, aryl, and chloroalkyl, and, together withthe ethylene moiety of the oxyethylene chain of Unit II, a saturatedcycloaliphatic hydrocarbon ring having from 4 to 8 carbon atoms, andabout 5 to about 99 weight percent of a nylon as the thermoplasticorganic polymer, said percentages being based on the total weight ofthermoplastic polymer and cyclic ester polymer.

2. Composition as claimed in claim 1 wherein said cyclic ester polymerconsists essentially of Units I.

3. Composition as claimed in claim 1 wherein said cyclic ester polymerconsists essentially of Units I and II.

4. Composition as claimed in claim 1 wherein said cyclic ester polymeris present in a minor weight amount and said thermoplastic organicpolymer is present in a major weight amount.

5. Composition as claimed in claim 1 wherein said cyclic ester polymeris present in the amount of about 2 to about 40 percent and saidthermoplastic organic polymer is present in the amount of about 60 toabout 98 percent based on the total weight of cyclic ester polymer andthermoplastic organic polymer.

6. Composition as claimed in claim 1 wherein said cyclic ester polymeris present in the amount of about to about percent and saidthermoplastic organic polymer is present in the amount of about 70 toabout 95 percent based on the total weight of cyclic ester polymer andthermoplastic organic polymer.

7. Composition as claimed in claim 1 wherein said cyclic ester polymeris characterized by the recurring structural recurring unit:

on E131 L \il, 1

value of from about 0.1 to about 15 and containing from g 100 to about 5mol percent of recurring linear Units I of the formula:

( R R O L x \R/y I wherein each R, individually, is selected from theclass consisting of hydrogen, alkyl, halo, and alkoxy; A is the oxygroup; 2: is an integer from 1 to 4; y is an integer from 1 to 4; z isan integer of zero or one; with the provisos that (a) the sum of x+y+zis at least 4 and not greater than 7, and (b) the total number of Rsubstituents which are substituents other than hydrogen does not exceed3; and from 0 to about 95 mol percent of recurring linear Units II ofthe formula:

(II) R'' R 32 drocarbon ring having from 4 to 8 carbon atoms; and (iii)said thermoplastic composition containing up to about 15 weight percentof said cyclic ester polymer, based on the total weight of said nylonand said cyclic ester polymer.

10. Composition as claimed in claim 9 (ii) wherein said Unit I has theformula:

wherein each R is hydrogen or methyl, with the proviso that no more thanthree R substituents are methyl groups; and (iii) wherein said Unit 11has the formula 101ml L 1: 11

wherein each R is hydrogen or lower alkyl.

11. Shaped and molded articles of the compositions claimed in claim 10:

(i) wherein said nylon is polycaprolactam;

(ii) wherein said cyclic ester polymer contains from about to about 10mol percent of recurring linear Units I and from about 30 to about molepercent of recurring linear Units II;

(iii) wherein the R substituent of Unit I is hydrogen;

(iv) wherein the R substituent of Unit II is hydrogen;

and

(v) wherein said composition contains from about one to about 10 Weightpercent of cyclic ester polymer, based on the total weight of saidcyclic ester polymer and said polyamide.

12. The articles of claim 11 which are in the form of fibers.

References Cited UNITED STATES PATENTS 3,299,171 1/1967 Knobloch 2607832,962,524 11/1960 Hostettler 26078.3 3,021,310 2/1962 COX 26078.33,021,311 2/1962 COX 26078.3 3,305,605 2/1967 Hostettler 26077.53,324,070 6/1967 Hostettler 26078.3 3,379,001 4/1968 Campbell 2608573,418,393 12/1968 King 260- 857 3,510,449 5/1970 Nagato 260857 FOREIGNPATENTS 22,351 9/1968 Japan 260-857 PE PAUL LIEBERMAN, Primary ExaminerUS. Cl. X.R.

2606, 13, 47 XA, 49, 823, 829, 830 R, 857 PA, 858, 874. 897 R, 898, 899,900

' UNITED STATES FATE @FFKCE CERTIFICATE @F QQECTION Patent No. 3,781,381Dated December 25, 1973 Invetom) J. v. Koleske et a1 It is certifiedthat error appears in the above-identif1ed patent and that said LettersPatent are hereby corrected as shown below:

Column 30, 1ines 1 9-52, should read Signed and sealed this 9th day ofApr'il 19714..

(SEAL) Attest:

EDWARD I-'I.FLETGHER,JR. I On MARSHALL DANN Attesting Officer iCommissioner of Patents

